Kinetics of the bulk polymerization of dioxolane in the presence of water

Abstract The polymerization of dioxolane initiated by the ∼Si⊕HSO ion pair is greatly influenced by water which changes the overall polymerization rate. Particularly great changes are brought about at certain higher conversions (whose values are also a function of an initial concentration of water). The polymerization practically stops at these conversions and the system appears to be close to a monomer—polymer equilibrium. It is shown that the equation Voverall = f([H2O]), which describes the dependence of the overall rate of polymerization on the concentration of water and which was originally derived for the polymerization of trioxane, holds also for the polymerization of dioxolane. The decrease of water concentration during the polymerization was measured and the observed equilibrium was shown to be a kinetic phenomenon.